DOE OSTI · 3017066
Connectivity-Dependent Exciton–Phonon Coupling in Cesium Bismuth Halide Quantum Dots
Abstract
Metal halide octahedra form the fundamental functional building blocks of metal halide perovskites, dictating their structures, optical properties, electronic structures, and dynamics. Here, in this study, we show that the connectivity of bismuth halide octahedra in Cs 3 Bi 2 Br 9 and Cs 3 Bi 2 I 9 quantum dots (QDs) changes with different halide elements. We use first-principles calculations to reveal the key role of the connectivity of bismuth halide octahedra on the wave function symmetry, Huang-Rhys factor, and exciton-phonon interaction strength. Following QD synthesis via a ligand-mediated transport method, the effect of connectivity is verified with transient absorption spectroscopy, where we contrast Cs 3 Bi 2 Br 9 and Cs 3 Bi 2 I 9 QD exciton dynamics. In photoexcited Cs 3 Bi 2 I 9 QDs, phonons related to the vibrational motions of face-sharing [BiI 6 ] 3- bioctahedra couple strongly to the electronic state and drive rapid carrier relaxation. Equivalent signals are not observed for photoexcited Cs 3 Bi 2 Br 9 QDs, implying a lack of phonon involvement in band-edge absorption and subsequent exciton relaxation. Our findings suggest that structural engineering can effectively tune the exciton-phonon coupling and therefore influence exciton relaxation and recombination in perovskite nanomaterials.
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Li, Beiye C. [Univ. of Chicago, IL (United States)] (ORCID:0000000267174318), Cairney, Hugh [Univ. of Chicago, IL (United States)] (ORCID:0000000233616659), Jin, Yu [Univ. of Chicago, IL (United States)] (ORCID:0000000260739953), Park, Jinsoo [Univ. of Chicago, IL (United States)], Sohoni, Siddhartha [Univ. of Chicago, IL (United States)], Lloyd, Lawson T. [Univ. of Chicago, IL (United States)], Liu, Yuzi [Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)] (ORCID:0000000287331683), Jureller, Justin E. [Univ. of Chicago, IL (United States)] (ORCID:0000000157602385), Ryu, Young Jay [Univ. of Chicago, IL (United States). Center for Advanced Radiation Sources (CARS)], Chariton, Stella [Univ. of Chicago, IL (United States). Center for Advanced Radiation Sources (CARS)], Prakapenka, Vitali B. [Univ. of Chicago, IL (United States). Center for Advanced Radiation Sources (CARS)], Schaller, Richard D. [Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM); Northwestern Univ., Evanston, IL (United States)], Galli, Giulia [Univ. of Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000280015290), Engel, Gregory S. [Univ. of Chicago, IL (United States)] (ORCID:0000000267405243). 2025-03-06. Connectivity-Dependent Exciton–Phonon Coupling in Cesium Bismuth Halide Quantum Dots. https://doi.org/10.1021/acsnano.4c18414
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